CN1249735A - Metal halide solid acids and supported metal halides as catalysts for preparation of hydrocarbon resins - Google Patents

Metal halide solid acids and supported metal halides as catalysts for preparation of hydrocarbon resins Download PDF

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Publication number
CN1249735A
CN1249735A CN98803202A CN98803202A CN1249735A CN 1249735 A CN1249735 A CN 1249735A CN 98803202 A CN98803202 A CN 98803202A CN 98803202 A CN98803202 A CN 98803202A CN 1249735 A CN1249735 A CN 1249735A
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monomer
raw material
metal halide
catalyzer
carrier
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劳拉·M·巴布科克
丹尼斯·G·莫雷尔
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Eastman Chemical Resins Inc
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Hercules LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerization Catalysts (AREA)
  • Catalysts (AREA)

Abstract

Supported metal halides and metal halide solid acids are used as catalysts for the polymerization of a feed stream containing at least one of pure monomer, C5 monomers, and C9 monomers to produce hydrocarbon resins. Freely-associated water may be removed from the solid acid catalyst prior to use. Resins with softening points (Ring and Ball) in the range of about 5 DEG C to 170 DEG C can be prepared. These catalysts offer advantages over the traditional Friedel-Crafts polymerization catalysts since the acid sites are an integral part of the solid. The solid acid catalysts are relatively nonhazardous, reusable catalysts which eliminate or at least reduce contamination of the resulting resin products with acid residues or by-products.

Description

Be used to prepare the metal halide solid acid of hydrocarbon resin and the metal halide catalyst on carrier
Related application
The application requires following preference according to 35U.S.C. § 119 (e): the U.S. Provisional Application No.60/035 of application on January 8th, 1997,217; The U.S. Provisional Application No.60/034 of application on January 9th, 1997,579; With the U.S. Provisional Application No.60/035 of application on January 10th, 1997,797; These apply for that disclosed full content is incorporated herein by reference at this.
Background of invention 1, invention field
The present invention relates to metal halide on carrier and metal halide solid acid as catalyzer, be used for making and contain pure monomer, C5 monomer and at least a polymerizable raw material of C9 monomer and prepare hydrocarbon resin; The invention still further relates to the metal halide that is used on the carrier and the method for metal halide solid acid Preparation of Catalyst hydrocarbon resin, and the hydrocarbon resin of producing in this way. 2, background discussion
Hydrocarbon resin is the low molecular weight thermoplastic by heat or catalytic polymerization preparation.This resinoid can be obtained by the monomer of several different sourcess.The monomer source comprises oil pyrolysis overhead product, turps cut (for example terpenes that is obtained by the natural product distillation), paper mill by product, coal tar and the various pure olefinic monomer of oil refining process.
The hydrocarbon resin that obtains can change to hard, crisp solid from heavy-gravity liquid, and its color can change to light yellow, amber or dark-brown from water white according to employed monomer and specific reaction conditions.Usually, it is water white that the resin of pure monomer tends to, and the C9 monomer resin tends to brown, and the C5 monomer resin tends to be yellow.
Hydrocarbon resin is widely used in tackiness agent, rubber, thermosol, printing-ink, coating, floor and other application as properties-correcting agent.This resinoid is commonly used to other material of modification.
The pure monomer hydrocarbon resin can pass through styrene-based monomers, for example vinylbenzene, alpha-methyl styrene, Vinyl toluene and other alkyl-substituted styrene, use the Friedel-Crafts polymerizing catalyst, for example be not carried on Lewis acid on the carrier (boron trifluoride (BF for example 3), boron trifluoride complex, aluminum chloride (AlCl 3), alkyl aluminum chloride), carry out cationoid polymerisation and prepare.
Similarly, aliphatics C5 hydrocarbon resin can be also referred to as " C5 monomer " by the oil pyrolysis raw material that contains C5 and C6 paraffinic hydrocarbons, alkene and diolefine, carries out cationoid polymerisation and prepares.These monomer material packages are drawn together the monomer that can carry out cationoid polymerisation, for example as the 1,3-pentadiene of principal reaction component, and cyclopentenes, amylene, 2-methyl-2-butene, 2-methyl-2-amylene, cyclopentadiene and Dicyclopentadiene (DCPD).Use the Friedel-Crafts polymerizing catalyst, for example be not carried on Lewis acid on the carrier (boron trifluoride (BF for example 3), boron trifluoride complex, aluminum chloride (AlCl 3) or alkyl aluminum chloride) catalytic polymerization.Except that reactive component, the not polymeric component in raw material comprise can with the stable hydrocarbon of unsaturated component condistillation, for example pentane, pentamethylene or 2-methylpentane.This raw material monomer can with C4 or C5 alkene or the dimer copolymerization as chain-transfer agent.
Aromatic series C9 hydrocarbon resin also can be also referred to as " C9 monomer " with the petroleum distillate deutero-aromatic C 8, C9 and/or the C10 unsaturated monomer that are obtained by naphtha cracking, carries out cationoid polymerisation and prepares.These monomer material packages are drawn together the monomer that can carry out cationoid polymerisation, for example other alkyl-substituted derivative of vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, Vinyl toluene, indenes, Dicyclopentadiene (DCPD), Vinylstyrene and these components.Use the Friedel-Crafts polymerizing catalyst, for example be not carried on Lewis acid on the carrier (boron trifluoride (BF for example 3), boron trifluoride complex, aluminum chloride (AlCl 3), alkyl aluminum chloride) catalytic polymerization.Except that reactive component, polymeric component does not comprise aromatic hydrocarbon, for example dimethylbenzene, ethylbenzene, isopropyl benzene, ethyltoluene, 1,2-indane, methyl indane, naphthalene and other similar species.In the raw material these not polymeric component can be incorporated into resin by alkylated reaction.
Although the Lewis acid that does not load on the carrier is the effective catalyst of the cationic polymerization of preparation hydrocarbon resin, they have some shortcomings.Traditional Lewis acid that does not load on the carrier is only expendable catalyzer, and it requires cancellation reaction and antacid production stage.
In addition, traditional Lewis acid that does not load on the carrier also requires to remove catalyzer salt resistates from the rosin products that obtains.In removing catalyzer and behind the salt resistates that produces, handle these resistatess and require extra-pay again.So, the amount of minimizing relict catalyst, particularly the amount of the Halogen species that produce in these reactions is to make us interested especially.
Use traditional Lewis acid catalyst that does not load on the carrier, for example AlCl 3And BF 3Another problem of being brought is that they are hazardous materials.These traditional Lewis acid catalysts produce the acid gas (for example HF, HCl) of high corrosion when being exposed to moisture.
Except that common Lewis acid, people have also done the work of some solid acid catalyst aspects.People such as BITTLES, " the cinnamic polymerization of clay catalyzed reaction I. of alkene ", Journal of Polymer Science:A part, the 2nd volume, 1221-31 page or leaf (1964), and people such as BITTLES, " the clay catalyzed reaction II. catalyzer of alkene acid and measure ", Journal of Polymer Science:A part, the 2nd volume, 1847-62 page or leaf (1964), its disclosed full content is incorporated herein by reference, they disclose together with acid clay catalyst styrene polymerization, obtain molecular weight and be 440～2000 polymkeric substance, and molecular weight is to measure with the depression of the freezing point method of benzole soln.These are used in the method that heats under the vacuum and prepare polymerizing catalyst according to the document, and if catalyzer absorbed moisture, by under vacuum once more the heating, can recover activity of such catalysts.
SALT, " activated clay in polymerization process as Application of Catalyst, the particularly polymkeric substance of alpha-methyl styrene ", Clay Minerals Bulletin, the 2nd volume, 55-58 page or leaf (1948), its disclosed full content is incorporated herein by reference, and the document discloses the use clay catalyst, makes vinylbenzene and/or alpha-methyl styrene polymerization, and obtaining from the dimer to the molecular weight is about 3000 polymkeric substance.
The 5th of people such as CHEN, 561, No. 095 the disclosed full content of United States Patent (USP) is incorporated herein by reference, this patent disclosure a kind of Lewis acid catalyst on carrier, be used for alkene, comprise the polymerization of the alpha-olefin of C3～C23, obtain number-average molecular weight (Mn) and be about 300～300,000 polymkeric substance.Typical Lewis acid vectors comprises silicon-dioxide, silica-alumina, zeolite and clay.People's such as CHEN embodiment 1 discloses a kind of Lewis acid that loads on the silicon-dioxide of heating under vacuum.
The 3rd of people such as WHEELER, 799, No. 913 the disclosed full content of United States Patent (USP) is incorporated herein by reference, this patent disclosure be used for the Friedel-Crafts catalyzer of polymerization polymerizable components, described polymerizable components comprises alpha-methyl styrene, indenes, Vinyl toluene and vinylbenzene, obtains number-average molecular weight (Mn) and is about 350～1200 polymkeric substance.Zinc chloride is disclosed as a kind of Friedel-Crafts catalyzer.
The 3rd of SAINES, 652, No. 707 the disclosed full content of United States Patent (USP) is incorporated herein by reference, this patent disclosure be used for the Friedel-Crafts metal halide catalyst of olefin polymerization, described alkene comprises amylene, vinylbenzene and vinyl toluene, obtains molecular weight and be about 700～2500 polymkeric substance.Zinc chloride is disclosed as a kind of Friedel-Crafts metal halide catalyst.
People such as PENG, " Electrophilic Polymerization of 1,3-PentadieneInitiated by Aluminum Triflate ", Eur.Polym.J, the 30th volume, the 1st, 69-77 page or leaf (1994), disclosed full content is incorporated herein by reference, and discloses the polymerization that trifluoromethanesulfonic acid aluminium (aluminum triflate) is used for 1,3-pentadiene, obtains the polymkeric substance of various number-average molecular weights.
The disclosed full content of european patent application 0352856A1 is incorporated herein by reference, this patent disclosure trifluoromethanesulfonic acid aluminium, trifluoromethanesulfonic acid cerium etc. be used for the oligomerization of C3～C6 alkene, obtain containing the oligomer of 6～24 carbon atoms.
People such as GANDINI, " The Heterogeneous Cationic Polymerization ofAromatic Monomers by Aluminum Triflate ", Polymer Preprints, AmericanChemical Society, 359-360 page or leaf (1996), disclosed full content is incorporated herein by reference, and discloses the polymerization that trifluoromethanesulfonic acid aluminium is used for the C9 relevant monomer, obtains number-average molecular weight (Mn) and is about 3000 polymkeric substance.This document also points out, trifluoromethanesulfonic acid aluminium can be used for direct " resinifying " of the mixture of the fragrant monomer that obtained by specific petroleum fractions and solvent.
Other open solid acid catalyst is used for the file that monomer polymerization prepares resin and comprises: the 4th of LEPERT, 068, the 4th of No. 062 United States Patent (USP), LEPERT, the 4th, 245 of 130, No. 701 United States Patent (USP)s, LEPERT, the 4th of No. 075 United States Patent (USP) and LUVINH, 824, No. 921 United States Patent (USP)s, their disclosed full contents are incorporated herein by reference.
Summary of the invention
The present invention relates to the preparation of hydrocarbon resin.More specifically, the present invention relates to use at least a in metal halide on carrier and the metal halide solid acid catalyzer to come the polymeric hydrocarbon raw material monomer.
At least a by in pure monomer, C5 monomer and the C9 monomer, but use the metal halide on carrier of mutually environment amenable recirculation and at least a preparation hydrocarbon resin in the metal halide solid acid catalyzer, the free associated water in the described catalyzer is removed.In the present invention, by cationoid polymerisation (for example Friedel-Crafts) preparation hydrocarbon resin, wherein preferably be used in the raw material that metal halide on the carrier and at least a processing in the metal halide solid acid catalyzer one of contain in pure monomer, C5 monomer and the C9 monomer at least.
Before use, handle solid acid catalyst and/or carrier to remove the free associated water of associating to solid, so that acidity of catalyst and polymerization activity are the highest.For example, before use, but the sufficiently long time of calcined catalyst and/or carrier removing free associated water, and/or make catalyzer and/or carrier be in decompression down.As example of incinerating, calcine the highest can under about 700 ℃ temperature, carrying out, preferably under 50～500 ℃ temperature, carry out.Calcining can under reduced pressure be about most 8 hours, preferred about 1～4 hour.
According to an aspect, the present invention relates to the preparation method of hydrocarbon resin, this method is included in the metal halide solid acid catalyzer that is carried on the carrier and exists down, make to comprise that the polymerizable raw material that one of is selected from pure monomer, C5 monomer and the C9 monomer at least produces hydrocarbon resin, wherein from described metal halide solid acid catalyzer on carrier, remove all freely associating basically.
According to an aspect, the present invention relates to the preparation method of hydrocarbon resin, this method is included in ZrCl 4Exist down, make to comprise that the polymerizable raw material that one of is selected from pure monomer, C5 monomer and the C9 monomer at least produces hydrocarbon resin.
Can be included in Lewis acid on clay, silicon-dioxide, silica-alumina, mesoporous silica, mesoporous silica-aluminum oxide, ion exchange resin, the zeolite at the metal halide solid acid catalyzer on the carrier.Lewis acid can comprise at least a acid that is selected from following group: ZnCl 2, AlCl 3, AlBr 3, BF 3, BCl 3, FeCl 3, SnCl 4, TiCl 4, ZrCl 4, HfCl 4, BiCl 3And lanthanide halides.
Clay carrier can comprise as naturally occurring clay mineral, for example at least a among kaolin, wilkinite, attapulgite, polynite, Clarit, Fuller's earth, hectorite and the Beidellite; Synthesis of clay, for example at least a in talcum powder and the hydrogenation talcum; The montmorillonite clay of handling with sulfuric acid or spirit of salt; And modified clay, for example aluminum oxide as the clay of pillar, cerium modified aluminum oxide as at least a as in the clay of pillar of the clay of pillar and metal oxide.
Zeolite support comprises and is selected from least a in following group: zeolite Y, zeolite beta, MFI, MEL, NaX, NaY, faujusite and mordenite.
According to another aspect of the present invention, the metal halide solid acid catalyzer on carrier comprises the aluminum halide of polymer graft.
According to another aspect of the present invention, raw material comprises the monomer of about 20 weight %～80 weight % and the solvent of about 80 weight %～20 weight %.Preferably include the monomer of about 30 weight %～70 weight % and the solvent of about 70 weight %～30 weight % in the raw material.More preferably comprise the monomer of about 50 weight %～70 weight % and the solvent of about 50 weight %～30 weight % in the raw material.Described solvent can comprise aromatic solvent.Aromatic solvent can comprise and is selected from least a in toluene, dimethylbenzene and the aromatic base crude oil solvent.Described solvent can comprise aliphatic solvent.The present invention can also comprise and recycles solvent.
According to one aspect of the present invention, comprise the C5 monomer in the raw material at least.Can comprise the C5 monomer at least in the described raw material, cyclopentadiene and methyl cyclopentadiene component are removed in wherein heating and distillation classification under 100～160 ℃ temperature thus from raw material.The C5 monomer can comprise and is selected from iso-butylene, 2-methyl-2-butene, 1-amylene, 2-Methyl-1-pentene, 2-methyl-2-amylene, 2-amylene, cyclopentenes, tetrahydrobenzene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,3-hexadiene, 1, in 4-hexadiene, cyclopentadiene and the Dicyclopentadiene (DCPD) one of at least.Can comprise the C5 monomer at least in the described raw material, wherein comprise polymerisable monomer in the raw material, wherein contain 1,3-pentadiene at least about 50 weight % at least about 70 weight %.The C5 raw material can contain the isoprene of low levels, contains some 2-methyl-2-butene usually, and can contain one or more cyclodiene.
Can comprise the C5 monomer at least in the described raw material, wherein also comprise the chain-transfer agent that is up to about 40 weight % in the raw material, preferably be up to the chain-transfer agent of about 20 weight %.Described chain-transfer agent can comprise and one of being selected from C4 alkene, C5 alkene, C4 dimerizing olefins body and the C5 dimerizing olefins body at least.Described chain-transfer agent can comprise and one of being selected from iso-butylene, 2-methyl-1-butene alkene, 2-methyl-2-butene, its dimer and the oligomer thereof at least.
According to one aspect of the present invention, comprise the C5 monomer of about 30 weight %～95 weight % and the auxiliary material of about 70 weight %～5 weight % in the raw material, this auxiliary material comprises and is selected from least a in pure monomer, C9 monomer and the terpenes.Preferably, comprise the C5 monomer of about 50 weight %～85 weight % and the auxiliary material of about 50 weight %～15 weight % in the raw material, this auxiliary material comprises and is selected from least a in pure monomer, C9 monomer and the terpenes.
According to another aspect of the present invention, comprise the C9 monomer in the described raw material at least.This C9 monomer can comprise and is selected from least a in vinylbenzene, Vinyl toluene, indenes, Dicyclopentadiene (DCPD) and the alkyl derivative thereof.Described C9 monomer can comprise the polymerizable unsaturated hydrocarbons at least about 20 weight %.Described C9 monomer can comprise the polymerizable unsaturated hydrocarbons of about 30 weight %～75 weight %.Described C9 monomer can comprise the polymerizable unsaturated hydrocarbons of about 35 weight %～70 weight %.
According to one aspect of the present invention, comprise the C9 monomer of about 30 weight %～95 weight % and the auxiliary material of about 70 weight %～5 weight % in the raw material, this auxiliary material comprises and is selected from least a in pure monomer, C5 monomer and the terpenes.Preferably, comprise the C9 monomer of about 50 weight %～85 weight % and the auxiliary material of about 50 weight %～15 weight % in the raw material, this auxiliary material comprises and is selected from least a in pure monomer, C5 monomer and the terpenes.
When the existing of controlled water gaging arranged in raw material monomer, many metal halide and metal halide solid acid catalyzer on carrier played a role most effectively.According to these characteristics of the present invention, should comprise the water that is lower than about 500ppm in the raw material, preferably be lower than the water of about 200ppm, more preferably less than the water of about 100ppm, most preferably be lower than the water of about 50ppm.
According to another aspect of the present invention, in batch reactor, make raw material with based on the about 0.5 weight %～30 weight % of monomer weight, preferred about 1 weight %～20 weight %, more preferably from about 3 weight %～15 weight %, most preferably from about the solid acid catalyst of 0.5 weight %～5 weight % contacts.
According to one aspect of the present invention, catalyzer is joined in the raw material.
According to another aspect of the present invention, raw material is joined in the slurries of catalyzer and solvent formation.Described raw material can pass through on the fixed bed of catalyzer.
According to another aspect of the present invention, raw material is in catalyst slurry joins reactor.
According to one aspect of the present invention, adopt continuous processing or interrupter method to carry out polyreaction.Under temperature of reaction, the reaction times of interrupter method is about 30 minutes～8 hours, preferred about 1～4 hour.
According to one aspect of the present invention, raw material is being made an appointment with-50 ℃～150 ℃, and preferred-20 ℃～100 ℃ approximately, polymerization under more preferably from about 0 ℃～70 ℃ the temperature of reaction.
According to another aspect of the present invention, polyreaction is stopped by from hydrocarbon resin, removing catalyzer.Can from hydrocarbon resin, remove catalyzer by filtering.Can from the fixed-bed reactor that comprise catalyzer, shift out hydrocarbon resin.
According to one aspect of the present invention, the strip, hydrocarbons resin is to remove unreacted monomer, solvent and low-molecular weight oligo body.Unreacted monomer, solvent and low-molecular weight oligo body can reclaim use.
According to one aspect of the present invention, from hydrocarbon resin solution, isolate hydrocarbon resin.
According to one aspect of the present invention, raw material comprises pure monomer at least, and the softening temperature of the hydrocarbon resin that obtains is about 5 ℃～170 ℃, and described softening temperature is to adopt ASTM-E28 " ring and ball apparatus softening temperature standard method of test (Standard Test Method for Softening Point by Ringand Ball Apparatus) " to measure.Raw material can comprise the C5 monomer at least, and the softening temperature of the hydrocarbon resin that wherein obtains is about 50 ℃～150 ℃.Raw material can comprise the C9 monomer at least, and the softening temperature of the hydrocarbon resin that wherein obtains is about 70 ℃～160 ℃.
According to one aspect of the present invention, raw material comprises pure monomer at least, wherein the number-average molecular weight of gained hydrocarbon resin (Mn) is about 400～2000, weight-average molecular weight (Mw) is about 500～5000, Z-average molecular weight (Mz) is about 500～10,000, and the polymolecularity of measuring with Mw/Mn (PD) is for about 1.2～3.5, and wherein Mn, Mw and Mz measure with size exclusion chromatography (SEC).
According to one aspect of the present invention, raw material comprises the C5 monomer at least, wherein the number-average molecular weight of gained hydrocarbon resin (Mn) is about 400～2000, weight-average molecular weight (Mw) is about 500～3500, Z-average molecular weight (Mz) is about 700～15,000, and the polymolecularity of measuring with Mw/Mn (PD) is for about 1.2～5, and wherein Mn, Mw and Mz measure with size exclusion chromatography (SEC).
According to another aspect of the present invention, raw material comprises the C9 monomer at least, wherein the number-average molecular weight of gained hydrocarbon resin (Mn) is about 400～1200, weight-average molecular weight (Mw) is about 500～2000, Z-average molecular weight (Mz) is about 700～6000, and the polymolecularity of measuring with Mw/Mn (PD) is for about 1.2～3.5, and is preferred 1.2～2.5, and wherein Mn, Mw and Mz measure with size exclusion chromatography (SEC).
According to another aspect of the present invention, hydrocarbon resin is a hydrogenant.
Accompanying drawing is briefly described
The present invention is with in the detailed Description Of The Invention below, and several the unrestricted accompanying drawings with reference to indicating further describe in detail, wherein:
Fig. 1-4 isogram that the regression analysis of various pure monomer resin polymerizations produces that drawn.
Detailed description of the Invention
In this content of explaining, only be for a little examples, purpose is that various embodiments of the present invention are discussed for example, and to have only those to believe be to principle of the present invention and the notion aspect is the most useful and the description of the easiest understanding just is suggested.In this, the details of the present invention that we explained only is to satisfy fundamentally to understand needs of the present invention, is those skilled in the art to be understood how to realize several forms of the present invention in practice.
Unless otherwise indicated, all percentage values in this application, all be be 100% value of being measured (weight) to example weight.30% 30 weight parts that are illustrated in per 100 weight part samples like this, for example.
Unless otherwise indicated, compound of mentioning or component comprise this compound or component itself, and with the combination of other compound or component, for example mixture of compound.
Before further discussing, the definition following term is to help to understand the present invention.
Solid acid (SOLID ACID): a kind of solid, it can make alkaline Hammett indicator change color, its pK a＜0.
Metal halide solid acid (METAL HALIDE SOLID ACID): a kind of covalent linkage that comprises is connected the solid acid of the metal on the halogen ion.
Metal halide solid acid on carrier (SUPPORTED METALHALIDESOLID ACID): comprise solid catalyst with the carrier of compound association, described compound comprises that covalent linkage is connected the metal on the halogen ion, and described carrier for example is silicon-dioxide, silica-alumina, clay, zeolite.
Hydrocarbon resin (HYDROCARBON RESIN): a kind of lower molecular weight (be number-average molecular weight be about 200～less than about 3000, (SEC) records by size exclusion chromatography) thermoplastic polymer, heat or catalyzed polymerization by oil pyrolysis distillment, terpenes, coal tar fraction or pure olefinic monomer are synthetic, and wherein a kind of in the monomer is the monomer of C5 or higher carbon number at least.
Pure monomer (PURE MONOMER): a kind of comprising by synthetic components that produce or highly purified monomer species, for example, vinylbenzene that gets by ethylbenzene or the alpha-methyl styrene that gets by cumene.
Pure monomer raw material (PURE MONOMER FEED STREAM): the composition that comprises the pure monomer species of arbitrary number.
C5 monomer (C5 MONOMERS): by refining of petroleum for example cracking derive and the component of coming, contain the unsaturated hydrocarbons that comprises C5 and/or C6 alkene species, under environmental stress in about 20～100 ℃ of boilings.
C9 monomer (C9 MONOMERS): by refining of petroleum for example cracking derive and the component of coming, contain unsaturated aromatic C 8, C9 and/or C10 alkene species, under environmental stress in about 100～300 ℃ of boilings.
Free associated water (FREELY-ASSOCIATED WATER): by associate water to solid acid catalyst of chemisorption and/or physical adsorption.
As general introduction of the present invention, the preparation of hydrocarbon resin is to contain by using at least a as catalyzer in metal halide on carrier and the metal halide solid acid, making that at least a raw material carries out cationoid polymerisation in pure monomer (for example styrene-based monomers), C5 monomer and the C9 monomer.The softening temperature (ring and ball method) of the resin of preparation is preferably about 5～170 ℃, more preferably about 30～150 ℃.These catalyzer are better than traditional Lewis acid polymerizing catalyst, because acidic site is the solid integral part, perhaps Lewis acid is carried on the solid.In addition, for the Lewis acid on carrier, described Lewis acid loads on the solid, and therefore can remove from reaction.
Have a look the present invention in more detail, hydrocarbon resin is by polyreaction preparation, wherein contains at least a contact the in raw material at least a in pure monomer, C5 monomer and the C9 monomer and metal halide on carrier and the metal halide solid acid catalyzer.Available metal halide on carrier and metal halide solid acid catalyzer in the present invention comprises but is not limited to following kind.Lewis acid on clay
Lewis acid on clay comprise as:
ZnCl 2
AlCl 3
AlBr 3
BF 3
FeCl 3
SnCl 4
TiCl 4
ZrCl 4
HfCl 4
BCl 3
BiCl 3
Lanthanon
The clay of load Lewis acid comprise as:
Naturally occurring clay mineral, for example
Kaolin
Wilkinite
Attapulgite
Polynite
Clarit
Fuller's earth
Hectorite
Beidellite
Synthesis of clay, for example
Talcum powder
The hydrogenation talcum
The montmorillonite clay of handling with sulfuric acid or spirit of salt
Modified clay (promptly replacing the clay of modification) by backbone element, for example
Aluminum oxide is as the clay of pillar
Cerium modified aluminum oxide is as the clay of pillar
Metal oxide is as the clay of pillar.Lewis acid on silicon-dioxide or silica-alumina, for example
ZnCl 2
AlCl 3
AlBr 3
BF 3
FeCl 3
SnCl 4
TiCl 4
ZrCl 4
HfCl 4
BCl 3
BiCl 3
The Lewis acid of lanthanon on mesoporous silica or silica-alumina, for example
ZnCl 2
AlCl 3
AlBr 3
BF 3
FeCl 3
SnCl 4
TiCl 4
ZrCl 4
HfCl 4
BCl 3
BiCl 3
The Lewis acid of lanthanon on ion exchange resin, for example
ZnCl 2
AlCl 3
AlBr 3
BF 3
FeCl 3
SnCl 4
TiCl 4
ZrCl 4
HfCl 4
BCl 3
BiCl 3
The Lewis acid of lanthanon on natural or synthetic zeolite
Lewis acid on zeolite comprise as:
ZnCl 2
AlCl 3
AlBr 3
BF 3
FeCl 3
SnCl 4
TiCl 4
ZrCl 4
HfCl 4
BCl 3
BiCl 3
Lanthanon
The zeolite of load Lewis acid comprise as:
Zeolite Y
Zeolite beta (being BEA)
MFI (for example " Zeolite Sacony Mobil-5 " (" ZSM-5 "))
MEL (for example " Zeolite Sacony Mobil-11 " (" ZSM-11 "))
NaX
NaY
Faujusite (being FAU)
The aluminum halide solid inorganic acid of mordenite (being MOR) polymer graft
ZrCl 4
HfCl 4
Lanthanide halides
As previously mentioned, above-mentioned metal halide and metal halide solid acid catalyzer on carrier is not that they are whole.Select to can be used among the present invention other the metal halide on carrier and during the metal halide solid acid catalyzer, as standard, the acidity of metal halide on carrier and metal halide solid acid catalyzer should surpass-3 with the Hammet number.
The example of above-mentioned lanthanide halides comprises ScCl 3, YCl 3, LaCl 3, YbCl 3, CeCl 3, PrCl 3, NdCl 3, NdBr 3, SmCl 3, EuCl 3, GdCl 3, TbCl 3, DyCl 3, HoCl 3, HoBr 3, ErCl 3, TmCl 3And LuCl 3
For zeolite, BEA, MFI, MEL, FAU and MOR title are the skeleton construction type IUPAC definition of zeolite.
The example of the aluminum halide of above-mentioned polymer graft is seen 5,409, No. 873 United States Patent (USP)s of people such as people's such as CHUNG the 5th, 414, No. 177 United States Patent (USP)s and CHUNG, and the content of these two parts of patent documentations is incorporated herein by reference at this.
Before use, handle solid acid catalyst and/or carrier,, make acidity of catalyst and polymerization activity the highest to remove free associated water.Can adopt various technology to remove free associated water, comprise thermal treatment, reduced pressure treatment, dry gas for example nitrogen or air handling or their combination.Although do not wish to be bound by theory, remove the strength of acid maximum that free associated water makes the Lewis acid catalyst, and make the polyreaction circulation ratio better.
By calcining the free associated water that to remove on solid acid catalyst and/or the carrier, this often means that metal halide solid acid and/or carrier are heated to higher temperature, and do not make the catalyzer fusing.Can be under inert atmosphere, for example under nitrogen or the dry air, or under reduced pressure, calcining metal halide solid acid and/or carrier.Calcining preferably was about most 8 hours or longer, and more preferably from about 1～4 hour, preferably the highest at about 700 ℃, more preferably under about 100～400 ℃ of temperature, carry out.
Free associated water from metal halide solid acid catalyzer and/or carrier are removed can come from the water (physical absorption water) or the hydroxyl (chemical absorbed water) that associate on metal halide solid acid catalyzer and/or carrier.Remove basically all free associated water and mean and remove all or all physical absorption waters basically, and remove most of at least chemical absorbed water.
For the metal halide acid catalyst on carrier, solid acid catalyst can mainly be made up of the metal halide such as the Lewis acid of the single type on the carrier of single type.But, can be included in single type on single type or the polytype carrier or any combination of polytype metal halide at the metal halide solid acid catalyzer on the carrier.
Before mixed carrier and metal halide, but calcinated support.The importance of calcinated support depends on metal halide before mixed carrier and metal halide.For example, for the AlCl on carrier 3, AlBr 3, BF 3, TiCl 4, HfCl 4, FeCl 3And BCl 3, calcining is very crucial.For the ZrCl on carrier 4And BiCl 3, calcining is important.On the contrary, for the FeCl on carrier 3And ZnCl 2, can carry out or not carry out the calcining of carrier.
Have been found that, by being controlled at least a calcination condition in metal halide on the carrier and the metal halide solid acid catalyzer, for example control temperature or time that calcining step carries out, physicals that can cutting gained resin, for example its softening temperature or its molecular weight.
When the existing of controlled water gaging arranged in raw material, many metal halide and metal halide solid acid catalyzer on carrier of the present invention played a role most effectively.For example should comprise the water that is lower than about 500ppm in the raw material, preferably be lower than the water of about 200ppm,, most preferably be lower than the water of about 50ppm more preferably less than the water of about 100ppm.
The pure monomer raw material can contain purified relatively styrene-based monomers, for example vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, 4-vinyl toluene and Vinyl toluene cut.Monomer can be with the form of pure component, perhaps uses with the form of the mixture of two or more raw material monomers, to provide the resin property that needs.Preferred mixture comprises the alpha-methyl styrene of about 20～90 weight % and one or more comonomers of about 80～10 weight %, the mixture of optimization styrene, Vinyl toluene, 4-vinyl toluene or these components.In addition, monomer of the present invention also can use other alkylating vinylbenzene, for example t-butyl styrene or styryl phenyl.If desired, raw material can carry out drying, and preferably contains the water that is less than about 200ppm, more preferably less than the water of about 100ppm, most preferably is less than the water of about 50ppm.
Under the situation of C5 resin, contain unsaturated C5 and/or C6 alkene in the petroleum and reach at about 20～100 ℃, preferred about 30～70 ℃ of following ebullient diolefine.In some cases, by heating and distillation classification slowly under 100～160 ℃ temperature, remove cyclopentadiene and methyl cyclopentadiene component in the raw material.Monomer in these raw materials can include but not limited to: alkene, for example iso-butylene, 2-methyl-2-butene, 1-amylene, 2-Methyl-1-pentene, 2-methyl-2-amylene and 2-amylene; Cycloolefin, for example cyclopentenes and tetrahydrobenzene; Diolefine, 1,3-pentadiene, 1 for example, 4-pentadiene, isoprene, 1,3-hexadiene and 1,4-hexadiene; Cyclodiene, for example alkyl-substituted derivative of cyclopentadiene, Dicyclopentadiene (DCPD) and these cyclodiene and codimers.Business-like this class raw material is including, but not limited to " Naphtha Petroleum 3 Piperylenes ", by Lyondell PetrochemicalCompany, Houston, TX obtains, common " 1,3-pentadiene enriched material " or " senior 1; 3-pentadiene enriched material ", the both is by Shell Nederland Chemie B.V., Hoogvilet, and the Netherlands obtains.The C5 raw material contains the polymerisable monomer at least about 70 weight % usually, wherein contains the 1,3-pentadiene at least about 50 weight %.The C5 raw material can contain the isoprene of low levels, contains the 2-methyl-2-butene usually, and can contain one or more cyclodiene.
Still about the C5 raw material monomer, except that reactive component, the not polymerizable components in raw material comprises the stable hydrocarbon with unsaturated component condistillation, for example pentane, pentamethylene or 2-methylpentane.This raw material monomer can with C4 or C5 alkene or its dimer copolymerization as chain-transfer agent.Add chain-transfer agent can so that to resin have lower molecular weight and narrower molecular weight distribution than the resin that only uses the monomer preparation.Chain-transfer agent causes point by the polymkeric substance of regenerating makes chain termination, thereby the chainpropagation of polymkeric substance is stopped.The component that can be used as chain-transfer agent in these reactions is including, but not limited to: iso-butylene, 2-methyl-1-butene alkene, 2-methyl-2-butene, and the dimer or the oligomer of these species.Chain-transfer agent can perhaps join in the reaction after the dilution in solvent with pure form.If desired, raw material can carry out drying, and preferably contains the water that is less than about 500ppm, more preferably less than the water of about 200ppm, most preferably is less than the water of about 50ppm.
Under the situation of C9 monomer resin, contain in the raw material under environmental stress at about 100～300 ℃ of unsaturated aromatic C 8s of ebullient, C9 and/or C10 monomers.Aromatic C 8-C10 raw material (being also referred to as the C9 raw material) can be obtained by the steam cracking of petroleum fractions.Monomer in these raw materials can be including, but not limited to the alkyl derivative of vinylbenzene, Vinyl toluene, indenes, Dicyclopentadiene (DCPD) and these components.Business-like this class raw material including, but not limited to: by Lyondell Petrochemical Company, Houston, " LRO-90 " that TX obtains, by DSM, Geleen, " the DSM C9 Resinfeed Classic " that the Netherlands obtains, by Dow Chemical Company of Midland, " RO-60 " and " RO-80 " that Michigan obtains, and by Dow Chemical Company of Temeuzen, " the Dow Resin Oil 60-L " that the Netherlands obtains.The C9 raw material contains usually at least about 20 weight %, preferred about 30～75 weight %, most preferably from about the polymerizable unsaturated hydrocarbons of 35～70 weight %.All the other are the aromatics of alkyl replacement normally, and they can be attached in the resin by alkylated reaction.If desired, raw material can carry out drying, and preferably contains the water that is less than about 500ppm, more preferably less than the water of about 200ppm, most preferably is less than the water of about 50ppm.
Raw material can be defined as pure monomer, C5 monomer or C9 monomer.As a kind of alternative, can be used in combination auxiliary material with the main raw material that pure monomer, C5 monomer or C9 monomer constitute.According to the difference of main raw material, pure monomer, C5 monomer, C9 monomer or even terpenes and arbitrary combination thereof, all can be used as auxiliary material.The terpenes raw material is including, but not limited to d-limonene, α-and beta-pinene, and limonene.The resin that is got by the mixture of main raw material and auxiliary material can be by the main raw material of about 30～95 weight % and the auxiliary material of about 70～5 weight %, preferably by the auxiliary material preparation of main raw material and about 50～15 weight % of about 50～85 weight %.
Polymer raw preferably contains the monomer of 20～80 weight % that have an appointment, more preferably contains the monomer of 30～70 weight % that have an appointment, most preferably contains the monomer of 40～70 weight % that have an appointment.Under the situation of C5 resin, raw material can contain the chain-transfer agent that is up to about 40 weight %, more preferably contains the chain-transfer agent that is up to about 20 weight %, and described chain-transfer agent discussion as above.Raw material also contains the solvent of 80～20 weight % that have an appointment, for example toluene, octane, high boiling point aromatic solvent, aliphatic solvent or mixed solvent.
About solvent, for the pure monomer polymerization, preferred solvent is an aromatic solvent.Usually can use toluene, dimethylbenzene or light aromatic base crude oil solvent, for example can be by Exxon ChemicalCompany, Houston, " Aromatic 100 " that TX obtains can be by Ashland ChemicalIncorporated, Columbus, " HiSol 10 " that OH obtains, and can be by Shell ChemicalCompany, Houston, " Cyclosol 53 " that TX obtains.These solvents can use fresh, also can use processing to reclaim.Described solvent contains the water that is less than about 200ppm usually, more preferably less than the water of about 100ppm, most preferably is less than the water of about 50ppm.
For the C5 polymerization, preferred solvent is an aromatic solvent.Common unreacted sylvic oil component reclaims as solvent by processing.Except that recovered solvent, can use toluene, dimethylbenzene or aromatic base crude oil solvent, for example can be by Exxon Chemical Company, Houston, " Solvesso 100 " that TX obtains, and can be by Shell Chemical Company, Houston, " the Shellsol A " that TX obtains.These solvents can use fresh, also can use processing to reclaim.Described solvent contains the water that is less than about 500ppm usually, more preferably less than the water of about 200ppm, most preferably is less than the water of about 50ppm.
For the C9 polymerization, preferred solvent is an aromatic solvent.Common unreacted sylvic oil component reclaims as solvent by processing.Except that recovered solvent, can use toluene, dimethylbenzene or aromatic base crude oil solvent, for example can be by Exxon Chemical Company, " Solvesso 100 " that Houston, TX obtain and can be by Shell Chemical Company, Houston, " the Shellsol A " that TX obtains.These solvents can use fresh, also can use processing to reclaim.Described solvent contains the water that is less than about 200ppm usually, more preferably less than the water of about 100ppm, most preferably is less than the water of about 50ppm.
About polymeric reaction condition, the first important variable is an at least a consumption in metal halide on carrier and the metal halide solid acid catalyzer.Based on monomer weight, at least a consumption is preferably about 0.1～30 weight % in metal halide on carrier and the metal halide solid acid catalyzer.For the pure monomer resin, at least a concentration is preferably about 0.1～15 weight % in metal halide on carrier and the metal halide solid acid, and more preferably about 0.5～10 weight % most preferably is about 0.5～8 weight %.For the C5 monomer, at least a concentration is preferably about 0.5～30 weight % in metal halide on carrier and the metal halide solid acid, and more preferably about 1～20 weight % most preferably is about 3～15 weight %.For the C9 monomer, at least a concentration is preferably about 0.5～30 weight % in metal halide on carrier and the metal halide solid acid, and more preferably about 1～20 weight % most preferably is about 3～15 weight %.
The second important variable is a reaction sequence in reaction, i.e. the order and the mode that are bonded to each other of reactant.In a kind of reaction sequence, catalyzer can be joined in the monomer solution gradually, simultaneously control reaction temperature.As a kind of mode that can select, in another kind of reaction sequence, monomer can be joined gradually in metal halide on carrier and the metal halide solid acid catalyzer at least a slurries that in solvent, form.For certain catalyzer feeding quantity and temperature of reaction,, obtain the lower resin of softening temperature basically when monomer is joined in the catalyst slurry.As will be below going through in the paragraph, monomer is joined resulting resin in the catalyst solution, compare, have lower molecular weight and narrow polymolecularity with catalyzer being joined in the monomer resulting resin, be Mw/Mn, these data are measured by size exclusion chromatography.
The molecular-weight average size exclusion chromatography of resin, promptly SEC measures.Analyzing the chromatographic column group of usefulness is made of in order four Waters " Ultrastyragel " post, its hole size is respectively 500,500,1000 and 100 dusts, (being respectively PartNos.WAT010571,010571,010572,010570), can be by Waters Corporation, Milford, MA obtains.Calculate by the peak elution time of the narrow molecular weight distributions poly styrene polymer of one group of standard and to demarcate molecular weight.The standard substance group comprises 18 standard substances, its peak molecular weight from 162 up to 43900.The peak molecular weight of narrow molecular-weight standard substance is defined as (MwMn) 1/2(ASTM testing method D3536-76).Typical curve is defined as one three degree polynomial curve, and promptly logMW is to V c/ V rCurve, V wherein cBe the elution volume of standard substance, and V rBe the elution volume of reference peak, reference peak is that the oxygen that is present in the injection solution with the dissolved air form is formed.Pillar and detection cell (Hewlett-Packard's differential refractometer) remain on 40 ℃.Solvent (moving phase) is a tetrahydrofuran (THF), and the Yoshinox BHT (BHT, 2,6 di tert butyl 4 methyl phenol) that contains 250ppm is as stablizer (the described tetrahydrofuran (THF) that contains BHT can be by Burdick and Jackson, Muskegon, MI acquisition).The moving phase holder is protected with helium, and the maintenance flow velocity is 1 ml/min.Under such condition, the elution time of BHT is 35.86 minutes.Sample dissolution is in tetrahydrofuran (THF), and 0.25%wt/vol, and in injection before (200 microlitre) advance chromatographic instrument is that " TEFLON " (tetrafluoroethylene) film filter of 0.45 micron filters by a hole size.The molecular weight of report is the molecular weight of " the suitable thing of polystyrene ", is calculated by typical curve.
For the pure monomer resin, number-average molecular weight (Mn) with the resin of the inventive method preparation is about 400～2000, weight-average molecular weight (Mw) is about 500～5000, Z-average molecular weight (Mz) is about 500～10,000, and the polymolecularity of measuring with Mw/Mn (PD) is typically about 1.2～2.5 for about 1.2～3.5.For the C5 hydrocarbon resin, number-average molecular weight (Mn) with the resin of the inventive method preparation is about 400～2000, weight-average molecular weight (Mw) is about 500～3500, Z-average molecular weight (Mz) is about 700～15,000, and the polymolecularity of measuring with Mw/Mn (PD) is typically about 1.2～3.5 for about 1.2～5.For the C9 hydrocarbon resin, number-average molecular weight (Mn) with the resin of the inventive method preparation is about 400～1200, weight-average molecular weight (Mw) is about 500～2000, Z-average molecular weight (Mz) is about 700～6000, and the polymolecularity of measuring with Mw/Mn (PD) is typically about 1.2～2.5 for about 1.2～3.5.
As previously mentioned, compare with catalyzer is joined in the monomer, monomer is joined to obtain narrower polymolecularity and lower molecular weight in the catalyst solution.Consider the influence of reaction sequence, if desired, use on carrier metal halide and the metal halide solid acid catalyzer at least a than using traditional Lewis acid Friedel-Crafts catalyzer that is not carried on the carrier, can obtain narrower polymolecularity.Be the consistency of the polymkeric substance in guaranteeing resin and finally using, narrow polymolecularity is important.
The 3rd important response variable is a temperature of reaction.In these reactions, polymeric reaction temperature can be-50～150 ℃, and still, more preferably about-20～100 ℃ of temperature of reaction most preferably are about 0～70 ℃.For pure monomer, temperature of reaction is preferably-50～100 ℃ approximately, more preferably about-20～75 ℃, most preferably is-10～60 ℃ approximately.For 5 monomers, temperature of reaction is preferably-50～100 ℃ approximately, more preferably about-20～75 ℃, most preferably is-10～70 ℃ approximately.For the C9 monomer, temperature of reaction is preferably about 0～150 ℃, more preferably about 10～120 ℃, most preferably is about 20～110 ℃.Temperature has a significant impact the performance of final resin.Under lower temperature of reaction, prepare resin with higher molecular weight and high softening-point.Reaction times under temperature of reaction is preferably about 30 minutes～8 hours, more preferably about 1～4 hour.
Polymerization process can be continuous, semicontinuous or batch technology, carries out in successive, back reaction device intermittently, that semi-continuous, fixed bed, fluidized-bed and piston flow are such.For example, in continuous processing, make monomer solution pass through fixed bed catalyst, or monomer and catalyst slurry are fed in the flow reactor together.
Can make reaction terminating by from product, going out at least a in metal halide on carrier and the metal halide solid acid catalyzer with physical method for separation.Physical sepn can make reaction soln be neutral.In addition, by simple filtration, or, can realize physical sepn by from catalyst fixed bed, isolating resin solution.Consequently, physical sepn easily and fully, make for many on carrier metal halide and the metal halide solid acid catalyzer at least a, in rosin products, do not stay acid and remainder catalyst.
Leaching as tartaric acid is possible, then requires neutralizing acid.This step so-called in the prior art " cancellation ".At least a in metal halide on carrier that requires cancellation and the metal halide solid acid catalyzer, the salt that its produces lacks than traditional Lewis acid catalyst.
Like this, use on carrier metal halide and the metal halide solid acid catalyzer at least a, make the needs take extra processing step to come cancellation reaction, catalyst neutralisation and from the finished product, to filter out catalyzer salt resistates become very little, or become and do not need.
In case at least a and resin solution are separated in metal halide on carrier and the metal halide solid acid catalyzer, just can the stripping resin solution to remove unreacted hydrocarbon, solvent and low-molecular weight oligo thing, they can reclaim by processing and use.When reacting with pure monomer, can from the present invention, obtain the water white resin, in initial monomers, productive rate is the highest can be to 99%.
The softening temperature of the resin that is obtained by the present invention is preferably about 5 ℃～170 ℃ usually, and more preferably about 30～150 ℃, described softening temperature is to adopt ASTM-E28 " ring and ball apparatus softening temperature standard method of test " (revision in 1996) to measure.For pure monomer, softening temperature is preferably about 5 ℃～170 ℃, more preferably about 50 ℃～150 ℃.For the C5 hydrocarbon resin, softening temperature is preferably about 5 ℃～170 ℃, more preferably about 50 ℃～150 ℃, most preferably is about 70～130 ℃.For the C9 hydrocarbon resin, softening temperature preferably is up to about 170 ℃, and softening temperature most preferably is about 70～160 ℃.If desired, use proper reaction conditions, but can also prepare stir-in resin or those at room temperature are the resin of liquid.
After the resins, can carry out hydrogenation subsequently to reduce colourity and to improve color stability.The hydrogenation of resin is known to widely in the prior art.About the hydrogenant discussion, can be with reference to the 5th, 491, No. 214 United States Patent (USP)s of DAUGHENBAUGH etc., its disclosed full content is incorporated herein by reference.
Resin of the present invention can be used as properties-correcting agent, is used in tackiness agent, sealing agent, printing-ink, protective coating, plastics, road sign, floor and is used as to dry-clean finishing composition again.
Of the present invention on carrier metal halide and the metal halide solid acid catalyzer at least a, than not by the Lewis acid of load (AlCl for example 3, AlBr 3, BF 3, BF 3Title complex, TiCl 4, and other be generally used for Friedel-Crafts polymeric Lewis acid) have some advantages.Many this advantages are because acidic site is solid catalyst or the result who loads on the integral part of the Lewis acid on the solid.
Load on the solid because acidic site is the integral part and the Lewis acid of solid catalyst, remainder catalyst is minimum to the pollution of rosin products or solvent.Consequently, at least a in metal halide on carrier and the metal halide solid acid catalyzer can not produce color owing to catalyst residue makes hydrocarbon resin.If the use styrene-based monomers, the gained resin can be water white.
At least a in the present invention's metal halide on carrier and the metal halide solid acid catalyzer can regenerate and recycle usually, therefore reduced the waste treatment amount of used catalyzer.On the contrary, do not typically used once catalyzer by the Lewis acid of load.
In addition, with traditional not by the Lewis acid catalyst of load BF for example 3And AlCl 3Compare, at least a in the present invention's metal halide on carrier and the metal halide solid acid catalyzer is not dangerous.Catalyzer of the present invention does not produce corrodibility or dangerous liquid state or gaseous acid usually when being exposed to moisture.
Also will further illustrate the present invention below with embodiment.Embodiment 1-17 relates to the pure monomer resin, and embodiment 18-53 relates to the C5 resin, and embodiment 54-79 relates to the C9 resin.These embodiment right and wrong are determinate, do not limit scope of the present invention.
Unless otherwise noted, all percentage ratios that occurred in an embodiment, umber etc. all are meant weight.
Embodiment 1-3
These embodiment illustrate the zinc chloride of working load on silicon-dioxide and come the polymerization pure monomer as catalyzer.
The Preparation of catalysts method is as follows: 20g SILVER REAGENT zinc chloride is dissolved in the 75-100ml methyl alcohol, be added into then synthetic amorphous silica slurries (" EP-12 " level, CrosfieldLimited, Warrington, England) in.Stirred this solution 1 hour.On rotatory evaporator, slowly remove and desolvate, avoid collapsing of mixture to rise.Behind the rotary evaporation, material should be free-pouring solid.With this solid under 2mmHg in 40 ℃ of heating 2 hours, then under 2mmHg in 100 ℃ of heating 2 hours, at last under 2mmHg in 140 ℃ of heating 1 hour, calcined catalyst thus.Before use, in being full of the gloves bag of nitrogen, handle catalyzer.
The circulation experiment of catalyzer carries out in 1 gal reactor of strap clamp cover, and this reactor is equipped with dull and stereotyped turbine(type)agitator, the coil pipe that spirals, sample hose, thermowell, still bottom valve and sintered-metal filter.Filter bits is in the bottom of sample hose and the still bottom valve place of reactor, and its nominal value is 7 microns.The jacket temperature of reactor is controlled at 0 ± 5 ℃.Above-mentioned zinc chloride catalyzer and the 1000g toluene on carrier of 35g is added in the reactor.The catalyst/toluene mixture is cooled to 0 ℃.
866g alpha-methyl styrene and the cinnamic mixture of 366g are pumped into described 1 gal reactor, its feed rate be in spiral coil cooling tube, feed-20 ℃ fluidic simultaneously, make temperature of reaction be controlled at 0 ± 5 ℃.Pumping into the monomeric time is 100 minutes.Reactor maintain again 0 ℃ 3 hours.By two original position strainers, described catalyzer is retained in the reactor.Between per two catalyst recirculation experiment, take out the 1g catalyzer, and add the new catalyzer of 1g.The aliquots containig of the reaction mixture that filters out is rotated evaporation preparing rosin products, and the final condition of rotary evaporation is 3mmHg pressure, 190 ℃.
Use same catalyzer,, carry out next one reaction in substantially the same mode.The productive rate and the performance of resin are listed in table 1.
Table 1
Embodiment Catalyzer Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
????1 ZnCl on silicon-dioxide 2 ??87％ ??135℃ ??1176 ??2407 ??4492
????2 The catalyzer that from embodiment 1, reclaims ??76％ ??142℃ ??1431 ??3268 ??6825
????3 The catalyzer that from embodiment 2, reclaims ??59％ ??142℃ ??1383 ??3467 ??7486
Embodiment 4-5
Following examples illustrate uses catalyzer to prepare pure monomer resin with styrene-based monomers and the zinc chloride on silica supports as catalyzer to monomer interpolation program.Preparation of catalysts
With 5.0g (0.037mol) zinc chloride (98%, Aldrich, Milwaukee, WI) be dissolved in 50ml methyl alcohol (SILVER REAGENT, Aldrich, Milwaukee, WI) in.In this methanol solution, add the 13.5g solid support material (" EP-12 " silicon-dioxide, Crosfield Catalysts, Warrington, England, this catalyzer oneself in a vacuum in 150 ℃ of calcinings, to remove excessive water, obtain the carrier of accurate weight).At room temperature stirred slurries 30 minutes.Under 2-5mmHg, in rotatory evaporator, remove and desolvate, obtain flowable powder by mild heat.Before use, in drying nitrogen in 150 ℃ of calcined catalysts 2 hours.Polyreaction
A 500ml there-necked flask is equipped with top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add the 86.6g alpha-methyl styrene (SILVER REAGENT, Aldrich, Milwaukee, WI), 36.6g vinylbenzene (SILVER REAGENT, Aldrich, Milwaukee, WI) and 36.6g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI).Monomer and solvent carry out drying as follows: just before monomer uses, make it pass through activated alumina column (Fischer8-16 order, 0.3g aluminum oxide/ml monomer) and carry out drying, toluene is used 3 dust molecular sieve dryings before use.
The ZnCl that 3.7g is as above made 2/ SiO 2Catalyzer is transferred under not dampish nitrogen atmosphere in the reinforced dropping funnel.Catalyzer is joined in the reactor in 15 minutes time by reinforced dropping funnel, and reaction flask cools off outward simultaneously, keeps the goal response temperature.In reaction times of 1-2 hour altogether under temperature of reaction stirring reaction solution.
After reaction finished, vacuum filtration at room temperature went out the catalyzer in the resin solution.With about 100ml toluene wash reaction flask and catalyzer filter cake.
After filtering out catalyzer, under 2-5mmHg pressure and 100 ℃, from resin solution, remove and desolvate.Sylvic oil is put into flask, and this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of preparation is listed in table 2.
Table 2
Embodiment Temperature of reaction Productive rate Softening temperature (ring and ball method) Molecular weight
??Mn ????Mw ??Mz
????4 ??0℃ ??69％ ????150℃ ??1770 ????4050 ??8250
????5 ??25℃ ??83％ ????122℃ ??960 ????1470 ??2430
Embodiment 6-16
The following examples illustrate uses vinylbenzene and alpha-methyl styrene as monomer, uses through the zinc chloride of incinerating on silicon-dioxide as catalyzer, by the performance range of the available resin of the present invention.Combine, the following example has defined half factor contrived experiment, contains 2 variablees.Variable in these experiments comprises temperature of reaction and catalyzer feeding quantity.Comprise that also the multiple point is with the estimating experiment error.Can use the result who from the following example, obtains, measure response value, generate a model equation according to these research variablees for each.Yan Jiu response value comprises productive rate, ring and ball softening point and by number-average molecular weight (Mn), weight-average molecular weight (Mw) and the defined molecular weight distribution of Z-average molecular weight (Mz) in these embodiments.Preparation of catalysts
With 20.0g (0.15mol) zinc chloride (98%, Aldrich, Milwaukee, WI) be dissolved in 300ml methyl alcohol (SILVER REAGENT, Aldrich, Milwaukee, WI) in.Adding 80g solid support material in this methanol solution (" EP-12 " silicon-dioxide, Crosfield Catalysts, Warrington, England).At room temperature stirred slurries 30 minutes.Under 2-5mmHg, in rotatory evaporator, remove and desolvate, obtain flowable powder by mild heat.Before use, 40 ℃ of calcined catalysts 2 hours, 100 ℃ of calcinings 1 hour, 150 ℃ of calcinings 2 hours, all calcinings were all carried out in a vacuum then.Polyreaction
A 500ml there-necked flask is equipped with top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add the 86.6g alpha-methyl styrene (SILVER REAGENT, Aldrich, Milwaukee, WI), 36.6g vinylbenzene (SILVER REAGENT, Aldrich, Milwaukee, WI) and 36.6g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI).Just before use, make styrene-based monomers pass through activated alumina column (Fischer 8-16 order, 0.3g aluminum oxide/ml monomer), carry out drying thus.Equally before use, toluene is with 3 dust molecular sieve dryings.
The catalyzer that as above makes is transferred under not dampish nitrogen atmosphere in the reinforced dropping funnel.Catalyzer is joined in the reaction in 15 minutes time by reinforced dropping funnel, and reaction flask cools off outward simultaneously, keeps the goal response temperature.Amounting in reaction times of 1 hour stirring reaction solution under temperature of reaction.
After reaction times finished, at room temperature vacuum filtration went out the resin solution of gained from catalyzer.The toluene drip washing of about 100ml of reaction flask and catalyzer filter cake.
After filtering out catalyzer, sylvic oil is put into flask, this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The reaction conditions of each embodiment is listed in table 3.The level code of each variable is-1,0 and 1, represents low, neutralization height respectively.Use the coding variate-value to help producing the model equation of each response value.Encoded radio all is included in the bracket.
Table 3
Embodiment Catalyzer feeding quantity (weight %) Temperature of reaction (℃) Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
??6 ????3.25(0) ????25(0) ????74％ ????118℃ ??910 ??1470 ??2420
??7 ????1(-1) ????50(1) ????72％ ????68℃ ??610 ??830 ??1130
??8 ????6(1) ????25(0) ????86％ ????100℃ ??960 ??1550 ??2630
??9 ????1(-1) ????0(-1) ????10％ ????142℃ ??1240 ??2080 ??4400
??10 ????3.25(0) ????50(1) ????73％ ????76℃ ??660 ??890 ??1220
??11 ????3.25(0) ????25(0) ????77％ ????125℃ ??1000 ??1680 ??2810
??12 ????6(1) ????50(1) ????18％ ????70℃ ??450 ??480 ??520
??13 ????3.25(0) ????0(-1) ????36％ ????131℃ ??1650 ??3100 ??5700
??14 ????1(-1) ????25(0) ????64％ ????133℃ ??1080 ??1680 ??2620
??15 ????6(0) ????0(-1) ????70％ ????139℃ ??2130 ??5490 ??11780
??16 ????3.25(0) ????25(0) ????63％ ????103℃ ??790 ??1150 ??2110
For each of each response value (product yield of steam stripped, ring and ball softening point, Mn molecular weight, Mw molecular weight and Mz molecular weight), the data in analytically showing with regression analysis.Process variable (temperature of reaction (TMP) and catalyzer feeding quantity (CAT)) is encoded to-1,0 and 1, represent respectively low, in and the high level.Based on the coding variable, obtain following regression model.Response value by model representation makes a variation ratio with R 2(adj)) list.Equation 1 resin yield %=72.8-29.3 (CAT) is (TMP) (TMP)-26.3 2
R 2(adj)=78.9% Equation 2Ring and ball softening point=110-33.0 (TMP)
R 2(adj)=82.1% Equation 3Ln[Mn]=6.86-0.537 (TMP)-0.214 (CAT) is (TMP)
R 2(adj)=93.7% Equation 4Ln[Mw]=7.32-0.780 (TMP)-0.385 (CAT) is (TMP)
R 2(adj)=94.0% Equation 5Ln[Mz]=7.81-1.02 (TMP)-0.45 (CAT) is (TMP)
R 2(adj)＝96.4％
Be listed in the performance that top regression equation can be used to all resins that the group reaction condition of predictive control variable in scope of experiment can access.Can make isogram with the research factorial effect, and the performance of the prepared resin of the various reaction conditionss of relatively being predicted of usefulness.The productive rate of sample, Mn, Mw and Mz molecular weight are shown in Fig. 1-4 to the isogram of catalyzer feeding quantity and temperature of reaction.
Embodiment 17
Present embodiment illustrates the aluminum chloride of use on carrier and comes polymerizing styrene base monomer as catalyzer.Preparation of catalysts
With 20.0g (0.15mol) aluminum chloride (40 orders, Vanchlor Co., Inc., Lockport, NY) be dissolved in 100ml toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) in, this toluene has been used 4 dust molecular sieve drying mistakes.With before aluminum trichloride solution contacts, at 40 ℃ of dry 80g solid support materials (" EP-12 " silicon-dioxide, Crosfield Catalysts, Warrington, England), and 100 ℃ of dryings 1 hour, 150 ℃ of dryings 2 hours, all dryings were all carried out in a vacuum then.Aluminum trichloride solution is added in the exsiccant solid support material, and at room temperature stirs the slurries 30 minutes of gained.Under 2-5mmHg, in rotatory evaporator, remove and desolvate, keep temperature simultaneously, obtain flowable powder near 40 ℃.Before use, in inert atmosphere, store and handle catalyzer.Polyreaction
A 500ml there-necked flask is equipped with top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add the 86.6g alpha-methyl styrene (SILVER REAGENT, Aldrich, Milwaukee, WI), 36.6g vinylbenzene (SILVER REAGENT, Aldrich, Milwaukee, WI) and 36.6g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI).Just before use, make styrene-based monomers pass through activated alumina column (Fischer 8-16 order, 0.3g aluminum oxide/ml monomer) and carry out drying.Toluene is used 3 dust molecular sieve dryings before use.
Calculate with monomer, the catalyzer that 2.5wt% as above makes is transferred under not dampish nitrogen atmosphere in the reinforced dropping funnel.Catalyzer is joined in the reaction in 15 minutes time by reinforced dropping funnel, and reaction flask cools off outward simultaneously, keeps 25 ℃ temperature.In reaction times of 1 hour altogether under temperature of reaction stirring reaction solution.
After reaction finished, vacuum filtration at room temperature went out the catalyzer in the resin solution.With about 100ml toluene wash reaction flask and catalyzer filter cake.
After filtering out catalyzer, sylvic oil is put into round-bottomed flask, this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of reaction conditions and preparation is as follows.
25 ℃ of temperature of reaction
Resin productive rate 24%
59 ℃ of softening temperatures (ring and ball method)
Molecular weight
Mn?????????????520
Mw?????????????600
Mz?????????????740
Embodiment 18-22
These embodiment shown zinc chloride on various carriers as catalyzer to polymerization 1,3-pentadiene enriched material--the influence of C5 raw material.Preparation of catalysts
With 27.3g (0.2mol) zinc chloride (98%, Aldrich, Milwaukee, WI) be dissolved in 300ml methyl alcohol (SILVER REAGENT, Aldrich, Milwaukee, WI) in.(" F-22 " and " F-6 " acid-treated clays is obtained from Engelhard, Iselin, NJ to add the 100g solid support material in this methanol solution; " K-10 " acid-treated clays is obtained from Sud Chemie, Munich, Germany; Perhaps " EP-12 " silicon-dioxide is obtained from Crosfield Catalysts, Warrington, England).At room temperature stirred slurries 30 minutes.Under 2-5mmHg, in rotatory evaporator, remove and desolvate, obtain flowable powder by mild heat.Before use, in drying nitrogen in 150 ℃ of calcined catalysts 2 hours.Polyreaction
A 500ml there-necked flask has top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add 60g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) and the zinc chloride on carrier that as above makes of 14g.Under agitation catalyst slurry is heated to 50 ℃.
With 140g 1,3-pentadiene enriched material (Naphtha Petroleum 3 " Piperylenes ", Lyondell Petrochemical Company, Houston, TX), by reinforced dropping funnel, in the reaction flask that joined nitrogen protection in 15 minutes.Just before use, the following drying of carrying out of monomer and solvent: solvent is with 4 dust molecular sieve dryings, and makes the 1,3-pentadiene enriched material pass through activated alumina column (Fischer 8-16 order, 0.3g aluminum oxide/ml monomer) to carry out drying.
In reaction times of 1 hour altogether at 50 ℃ of following stirring reaction solution.Vacuum filtration at room temperature goes out the catalyzer in the resin solution.In vacuum (2-5mmHg),, remove volatile component and solvent thus 50 ℃ of following reacting by heating solution 2 hours.The flask fit on is cooperated the still head and the thermometer of the band adapter of inlet tube, and be connected to condenser and receiving bottle.Under nitrogen gas stream, the sylvic oil in this flask is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of preparation is listed in table 4.Embodiment 18-21 is according to the present invention, and comparing embodiment 22 is to be used for the comparison purpose.
Table 4
Embodiment Catalyzer Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
????18 ZnCl on the F-22 clay 2 ??13％ ??40℃ ?1520 ?2710 ?6500
????19 ZnCl on the F-6 clay 2 ??28％ ??41℃ ?1400 ?2490 ?6760
????20 ZnCl on the K-10 clay 2 ??13％ ???- ?1160 ?2180 ?5160
????21 ZnCl on EP12 silicon-dioxide 2 ??64％ ??44℃ ?1350 ?2360 ?4320
????22 Not by the ZnCl of load 2 ??0％ ???- ??- ??- ??-
Embodiment 23-25
These embodiment illustrate temperature of reaction to polymerization 1,3-pentadiene enriched material--the influence of C5 raw material, wherein use zinc chloride on silicon-dioxide as catalyzer.
Reaction method and embodiment 18-22 are similar.Catalyst system therefor is the zinc chloride (prepared as above-mentioned embodiment 7) on " EP12 " silicon-dioxide.Change temperature of reaction as shown in table 5 below, the character of gained resin also is listed in the table 5.
Table 5
Embodiment Catalyzer and temperature of reaction Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
????23 ??ZnCl 2/SiO 2-50℃ ??50％ ??30℃ ?1000 ?1710 ?3260
????24 ??ZnCl 2/SiO 2-25℃ ??29％ ??27℃ ?1410 ?2300 ?3600
????25 ??ZnCl 2/SiO 2-0℃ ??14％ ??31℃ 1480 ?2640 ?4360
Embodiment 26-36
These embodiment illustrate the zinc chloride feeding quantity on the silicon-dioxide and in reaction total zinc feeding quantity to the influence of polymerization 1,3-pentadiene enriched material-C5 raw material.In monomer, when the zinc chloride of constant density, the zinc chloride feeding quantity on silicon-dioxide is low more, and the productive rate of resin is high more.For zinc chloride feeding quantity given on the silicon-dioxide, catalyzer is many more with respect to monomeric feeding quantity, and then productive rate is high more.The Preparation of catalysts catalyst A
As the zinc chloride of preparation on silicon-dioxide as described in the embodiment 21.Catalyst B
With 13.7g (0.059mol) zinc chloride (98%, Aldrich, Milwaukee, WI) be dissolved in 150ml methyl alcohol (SILVER REAGENT, Aldrich, Milwaukee, WI) in.Adding 25g solid support material in this methanol solution (" EP-12 " silicon-dioxide is obtained from Crosfield Catalysts, Warrington, England).At room temperature stirred slurries 30 minutes.Under 2-5mmHg, in rotatory evaporator, remove and desolvate, obtain flowable powder by mild heat.Before use, in drying nitrogen in 150 ℃ of calcined catalysts 2 hours.Catalyzer C, D and E
The method that key is similar to the preparation method of catalyst B prepares catalyzer C-E.The zinc chloride feeding quantity of each catalyzer is as follows respectively: catalyzer C is 20.5g, and catalyzer D is 27.3g, and catalyzer E is 34.2g, wherein uses 25g silicon-dioxide.Polyreaction
As preparation resin as described in the embodiment 18-22.Catalyzer and catalyzer feeding quantity see Table 6, and the character of gained resin also is listed in the table 6.
Table 6
Embodiment Catalyzer Catalyzer feeding quantity wt% ?ZnCl 2Feeding quantity wt% Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
??26 ????A ????10 ?????2.1 ??64％ ??44℃ ??1350 ??2360 ??4320
??27 ????B ????3.6 ?????1.3 ??23％ ??39℃ ??1630 ??3000 ??5400
??28 ????B ????6.1 ?????2.1 ??26％ ??43℃ ??1690 ??3050 ??5390
??29 ????B ????10 ?????3.5 ??39％ ??42℃ ??1540 ??2810 ??4960
??30 ????C ????3.4 ?????1.5 ??12％ ??21℃ ??1370 ??2290 ??4930
??31 ????C ????4.8 ?????2.1 ??21％ ??25℃ ??1410 ??2220 ??3750
??32 ????C ????10 ?????4.5 ??34％ ??19℃ ??1270 ??1990 ??3110
??33 ????D ????2.5 ?????1.3 ??6％ ??41℃ ??1890 ??3660 ??6810
??34 ????D ????4.1 ?????2.1 ??11％ ??38℃ ??1790 ??3270 ??5820
??35 ????D ????10 ?????5.2 ??27％ ??39℃ ??1550 ??2970 ??5560
??36 ????E ????3.7 ?????2.1 ??7％ ??25℃ ??1520 ??2540 ??4480
Embodiment 37-39
These embodiment illustrate the metal halide that do not load on the carrier as catalyzer to polymerization 1,3-pentadiene enriched material--the influence of C5 raw material.Particularly, these embodiment have compared solid acid catalyst ZrCl 4With conventional Lewis acid FeCl 3And AlCl 3Effect.
A 500ml there-necked flask has top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add 30g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) and the metal halide catalyst of 0.008mol, FeCl 397%, ZrCl 499.9+% (these two kinds of reagent all are obtained from Aldrich, Milwaukee, WI) and AlCl 3(Vanchlor Co., Inc., Lockport, NY).Under agitation catalyst slurry is heated to 50 ℃.
With 100g 1,3-pentadiene enriched material (Naphtha Petroleum 3 " Piperylenes ", Lyondell Petrochemical Company, Houston, TX), by reinforced dropping funnel, in the reaction flask that joined nitrogen protection in 15 minutes.Just before use, the following drying of monomer and solvent:, and make the 1,3-pentadiene enriched material carry out drying by activated alumina column (Fischer8-16 order, 0.3g aluminum oxide/ml monomer) with 4 dust molecular sieve drying solvents.
In reaction times of 2 hours altogether at 50 ℃ of following stirring reaction solution.From reaction soln, remove catalyst solid by filtering.After the filtration, use 4ml NH 4The solution cancellation reaction soln of OH in 100ml water removes by separating funnel then and anhydrates.After the cancellation, at room temperature from resin solution, be separated in the catalyzer salt that forms during the cancellation by filtering.
Sylvic oil is put into round-bottomed flask, and this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of preparation is listed in table 7.Embodiment 37 and 39 carries out according to the present invention, and embodiment 38 is used for comparison.
Table 7
Embodiment Catalyzer Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
????37 ????FeCl 3 ????7％ 1 ?????- ??950 ??3750 ??16910
????38 ????AlCl 3 ????52％ ????95℃ ??1580 ??3120 ??6790
????39 ????ZrCl 4 ????52％ ????68℃ ??2250 ??5730 ??15160
1: sample is without stripping
Embodiment 40-44
These embodiment illustrate metal halide on carrier as catalyzer to the polymerization 1,3-pentadiene--the influence of C5 raw material.The ZnCl of Preparation of catalysts on carrier 2And FeCl 3
With 6g zinc chloride 98% or iron(ic) chloride 97% (all be obtained from Aldrich, Milwaukee, WI) be dissolved in 100ml methyl alcohol (SILVER REAGENT, Aldrich, Milwaukee, WI) in.Adding 24g solid support material in this methanol solution (" EP-12 " silicon-dioxide is obtained from CrosfieldCatalysts, Warrington, England).At room temperature stirred slurries 30 minutes.Under 2-5mmHg, in rotatory evaporator, remove and desolvate, obtain flowable powder by mild heat.Before use, in drying nitrogen in 150 ℃ of calcined catalysts 2 hours.BiCl on carrier 3, AlCl 3And ZrCl 4
Use following thermal cycling dried silica solid support material (" EP-12 " silicon-dioxide in vacuum (2-5mmHg), be obtained from Crosfield Catalysts, Warrington, England): following 1.5 hours of room temperature following half an hour, 35-40 ℃ following 1 hour, 100 ℃ and 150 ℃ are following 2 hours.Carrier with drying under inert atmosphere is added in the reaction flask, and the desirable metal halide of 6g is housed in this flask, and (bismuth chloride or zirconium tetrachloride all are obtained from Aldrich, Milwaukee, WI; Aluminum chloride is obtained from Vanchlor Chemical, Inc., and Lockport, NY).With syringe 100ml toluene is added in the solid.At room temperature stirred catalyst slurry 1 hour, and in vacuum (2-5mmHg), remove then and desolvate, and maintenance was near 20 ℃ temperature.Under room temperature and vacuum, be connected dry flowable solid 3 hours.Polyreaction
A 500ml there-necked flask has top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add 30-50g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) and the metal halide on support of the catalyst that as above makes of 0.011mol.Under agitation catalyst slurry is heated to 50 ℃.
With 100g1, and 3-pentadiene enriched material (Naphtha Petroleum 3 " Piperylenes ", Lyondell Petrochemical Company, Houston, TX), by reinforced dropping funnel, in the reaction flask that joined nitrogen protection in 15 minutes.Just before use, the following drying of monomer and solvent:, and make the 1,3-pentadiene enriched material carry out drying by activated alumina column (Fischer8-16 order, 0.3g aluminum oxide/ml monomer) with 4 dust molecular sieve drying solvents.
In reaction times of 2 hours altogether at 50 ℃ of following stirring reaction solution.From reaction soln, remove catalyst solid by filtering.After the filtration, use 4ml NH 4The solution cancellation reaction soln of OH in 100ml water removes by separating funnel then and anhydrates.After the cancellation, at room temperature from resin solution, be separated in the catalyzer salt that forms during the cancellation by filtering.
Sylvic oil is put into round-bottomed flask, and this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of preparation is listed in table 8.
Table 8
Embodiment Catalyzer Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
????40 ??BiCl 3/SiO 2 ????11％ ?????- ??1290 ??1900 ??6300
????41 ??ZnCl 2/SiO 2 ????37％ ????42℃ ??1780 ??2990 ??5340
????42 ??FeCl 3/SiO 2 ????7％ ?????- ??950 ??2360 ??10800
????43 ??AlCl 3/SiO 2 ????41％ ?????54℃ ??950 ??1490 ??2410
????44 ??ZrCl 4/SiO 2 ????55％ ?????60℃ ??1310 ??2570 ??4650
Comparative Examples 45
This Comparative Examples illustrate as the silicon-dioxide of the carrier of metal halide catalyst synthetic for the C5 hydrocarbon resin be not effective catalyzer.Polyreaction
A 500ml there-necked flask has top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.Be equipped with in this flask 60.0g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) and 14.0g silicon-dioxide (" EP-12 " silicon-dioxide is obtained from Crosfield Catalysts, Warrington, England).Before use, solvent is with 4 dust molecular sieve dryings.Under agitation catalyst slurry is heated to 50 ℃.
(Houston TX) is added in the flask of nitrogen protection for Naphtha Petroleum 3 " Piperylenes ", Lyondell Petrochemical Company with 140g 1,3-pentadiene enriched material in 15 minutes time by dropping funnel.Before use, make the 1,3-pentadiene enriched material carry out drying by activated alumina column (Fischer8-16 order, 0.3g aluminum oxide/ml monomer).Reaction soln is stirring under 50 ℃ in reaction times of 1 hour altogether.
Reaction at room temperature filters out silicon-dioxide by vacuum filtration after finishing from resin solution.Volatile matter is removed in decompression under 50 ℃, does not have product to stay.
Embodiment 46-49
Present embodiment illustrates to be reused the zirconium tetrachloride load on the silicon-dioxide and comes polymerization 1,3-pentadiene enriched material--C5 raw material as catalyzer.Preparation of catalysts
Use following thermal cycling dried silica solid support material (" EP-12 " silicon-dioxide in vacuum (2-5mmHg), be obtained from Crosfield Catalysts, Warrington, England): following 1.5 hours of room temperature following half an hour, 35-40 ℃ following 1 hour, 100 ℃ and 150 ℃ are following 2 hours.Carrier with drying under inert atmosphere is added in the reaction flask, be equipped with in this flask zirconium tetrachloride (Aldrich, Milwaukee, WI).For 10% catalyzer, feeding quantity is 3g zirconium tetrachloride and 27g silicon-dioxide; For 5% catalyzer, feeding quantity is the high and 57g silicon-dioxide of 3g tetrachloroization.With syringe 100ml toluene is added in the solid, this toluene is dry on 4 dust molecular sieves.At room temperature stirred catalyst slurry 1 hour, and in vacuum (2-5mmHg), remove then and desolvate, and maintenance was near 20 ℃ temperature.Under room temperature and vacuum, continued dry flowable solid 3 hours.Polyreaction
A 500ml there-necked flask has top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add 70g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) and following catalyzer.Before use, solvent is with 4 dust molecular sieve dryings.For 10% catalyzer, add that 25.6g as above makes at supported catalyst.For 5% catalyzer, add that 51.2g as above makes at supported catalyst.In all cases, in solution, add the metal chloride of 2.56g (0.001mol)--zirconium tetrachloride.Under agitation catalyst slurry is heated to 50 ℃.
With 100g 1,3-pentadiene enriched material (Naphtha Petroleum 3 " Piperylenes ", Lyondell Petrochemical Company, Houston, TX), by reinforced dropping funnel, in the reaction flask that joined nitrogen protection in 15 minutes.Before use, make the 1,3-pentadiene enriched material carry out drying by activated alumina column (Fischer8-16 order, 0.3g aluminum oxide/ml monomer).In reaction times of 2 hours altogether, at 50 ℃ of following stirring reaction solution.
Example as recycling makes catalyst deposit, and removes reaction soln with syringe from flask.With 100ml dry toluene washing catalyst, still this toluene is removed from catalyzer with syringe.In aforesaid catalyzer, add other solvent and monomer.
For all embodiment, after finishing in the reaction times, from reaction soln, remove catalyst solid by filtering.After the filtration, use 4ml NH 4The solution cancellation reaction soln of OH in 100ml water removes by separating funnel then and anhydrates.After the cancellation, at room temperature from resin solution, be separated in the catalyzer salt that forms during the cancellation by filtering.
Sylvic oil is put into round-bottomed flask, and this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of preparation is listed in table 9.
Table 9
Embodiment Catalyzer Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
????46 ?10％ZrCl 4/SiO 2 ????43％ ????63℃ ??1890 ??3830 ??8490
????47 ?10％ZrCl 4/SiO 2Recycle ????47％ ????56℃ ??1940 ??4020 ??8200
????48 ?5％ZrCl 4/SiO 2 ????35％ ????57℃ ??1450 ??2910 ??6860
????49 ?5％ZrCl 4/SiO 2Recycle ????59％ ????49℃ ??1440 ??3170 ??7460
Embodiment 50 and 51
These embodiment illustrate the aluminum trichloride catalyst of working load on aluminum oxide and come the polymerization 1,3-pentadiene--the C5 raw material monomer.Polyreaction
A 500ml there-necked flask has top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add 40g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) and the aluminum trichloride catalyst that is carried on the solid as described below--" CAT-59 " catalyzer (UOP, Des Plains, IL).
Before use, solvent is with 4 dust molecular sieve dryings.Before use also with the break-up of catalyst powdered.All catalyst treatment are all carried out in nitrogen.Under agitation catalyst slurry is heated to 50 ℃.
With 100g 1,3-pentadiene enriched material (Naphtha Petroleum 3 " Piperylenes ", Lyondell Petrochemical Company, Houston, TX), by reinforced dropping funnel, in the reaction flask that joined nitrogen protection in 15 minutes.Just before use, make the 1,3-pentadiene enriched material carry out drying by activated alumina column (Fischer8-16 order, 0.3g aluminum oxide/ml monomer).In reaction times of 1 hour altogether, at 50 ℃ of following stirring reaction solution.
After finishing in the reaction times, from reaction soln, remove catalyst solid by filtering.After the filtration, use 4ml NH 4The solution cancellation reaction soln of OH in 100ml water removes by separating funnel then and anhydrates.After the cancellation, at room temperature from resin solution, be separated in the catalyzer salt that forms during the cancellation by filtering.
Water washs the resin solution of gained to neutral pH, then in sal epsom (SILVER REAGENT, Aldrich, Milwaukee, WI) middle drying.Sylvic oil is put into round-bottomed flask, and this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of preparation is listed in table 10.
Table 10
Embodiment Catalyzer Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
????50 27wt%CAT-59 is in monomer ??50％ ???62℃ ??1510 ??2900 ??5950
????51 13.5wt%CAT-59 is in monomer ??27％ ???62℃ ??1640 ??3320 ??6980
Embodiment 52 and 53
These embodiment illustrate the synthetic aluminum chloride of use on carrier and come polymerization 1,3-pentadiene enriched material--C5 raw material as catalyzer.Preparation of catalysts
With 7.5g (0.06mol) aluminum chloride (40 orders, Vanchlor Co., Inc., Lockport, NY) and 30g " EP-12 " silicon-dioxide (Crosfield Catalysts, Warrington, England) with 180ml toluene (Aldrich, Milwaukee WI) mixes this toluene and has used 4 dust molecular sieve dryings.With before aluminum trichloride solution contacts, following drying support material: following 2 hours of 40 ℃ following 2 hours, 100 ℃ following 1 hour and 150 ℃, all dryings are all carried out in a vacuum.Aluminum trichloride solution is added in the solid support material of drying, at room temperature stirred catalyst slurry then 1 hour.In vacuum (2-5mmHg), remove and desolvate, and maintenance is near 25-30 ℃ temperature, to obtain flowable powder.Before use, in inert atmosphere, store and handle catalyzer.Polyreaction
Prepare resin as embodiment 50 and 51 described methods.The performance of the resin of preparation is listed in table 11.
Table 11
Embodiment Catalyzer Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
??52 ?27wt％Al 3/SiO 2, in monomer ????21％ ????54℃ ??960 ??1330 ??2010
??53 ?3.75wt％Al 3/SiO 2, in monomer ????26％ ????47℃ ??1030 ??1540 ??2610
Embodiment 54-58
These embodiment illustrate the zinc chloride of use on various solid support materials as solid acid catalyst, by the unsaturated aromatic hydrocarbon feedstock production of C9 hydrocarbon resin.
Be prepared as follows the zinc chloride catalyzer on carrier.With the 27.3g zinc chloride (Aldrich, Milwaukee, WI) be dissolved in 300ml methyl alcohol (SILVER REAGENT, Aldrich, Milwaukee, WI) in.In this methanol solution, add the 100g solid support material, and stirred slurries 30 minutes.Used solid support material is " F-22 " and " F-6 " clay (Engelhard Corporation, Iselin, NJ), " K-10 " clay (Sud Chemie/United Catalyst Inc., Louisville, KY) and " EP-12 " silicon-dioxide (Crosfield Catalysts, Warrington, England).Methyl alcohol is removed in decompression from catalyzer in rotatory evaporator.Before use, in drying nitrogen in 150 ℃ of calcined catalysts 2 hours.
A 500ml there-necked flask has top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add 50g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) and the zinc chloride on carrier that as above makes of 15wt%.
(be obtained from Lyondell PetrochemicalCompany, Houston TX), joins in the reaction flask by reinforced dropping funnel with 100g C9 raw material monomer " LRO-90 ".Just before use, the following drying of carrying out of monomer and solvent: make the C9 raw material monomer carry out drying by activated alumina column (Fischer8-16 order, 0.3g aluminum oxide/ml monomer).Also use 3 dust molecular sieve drying toluene before use.
Reaction soln is heated to 50 ℃ temperature of reaction.By reinforced dropping funnel monomer is added in the reaction flask, it adds speed should be able to keep the desired response temperature under the refrigerative situation outside having.The monomer interpolation time is about 15 minutes.In reaction times of 2 hours altogether under the desired response temperature stirring reaction solution.
After finishing in the reaction times, at room temperature from acid-treated clay catalyst, isolate resin solution by vacuum filtration.With about 100ml toluene drip washing reaction flask and catalyzer filter cake.
Behind the filtering catalyst, under vacuum (2-5mmHg) and 100 ℃, from resin solution, remove and desolvate.Sylvic oil is put into a round-bottomed flask, and this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of preparation is listed in table 12.Embodiment 54-57 is according to the present invention, and comparing embodiment 58 is to be used for the comparison purpose.
Table 12
Embodiment Catalyzer Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz
????54 ????ZnCl 2/F-22 ????29％ ??121℃ ??680 ??960 ?1390
????55 ????ZnCl 2/K10 ????39％ ??101℃ ??540 ??800 ?1230
????56 ????ZnCl 2/EP12 ????38％ ??113℃ ??590 ??850 ?2590
????57 ????ZnCl 2/F-6 ????40％ ??124℃ ??690 ??960 ?1410
????58 ????ZnCl 2 ????0％ ???- ??- ??- ??-
Embodiment 59-72
These embodiment illustrate zinc chloride catalyzer and the catalyzer feeding quantity that is carried on the silicon-dioxide under various temperature of reaction, to the influence of the character of prepared C9 resin.Preparation of catalysts
With 5.0g (0.037mol) zinc chloride (98%, Aldrich, Milwaukee, WI) be dissolved in 50ml methyl alcohol (SILVER REAGENT, Aldrich, Milwaukee, WI) in.(" EP-12 " silicon-dioxide is obtained from Crosfield Catalysts, Warrington to add the 13.5g solid support material in this methanol solution, England, this silicon-dioxide oneself under vacuum in 150 ℃ of calcinings, to remove excessive water, obtain the carrier of accurate weight).At room temperature stirred slurries 30 minutes.In the vacuum of 2-5mmHg, in rotatory evaporator, remove methyl alcohol, obtain flowable powder by mild heat.Before use, in drying nitrogen in 150 ℃ of calcined catalysts 2 hours.Polyreaction
A 500ml there-necked flask has top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add 50g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) and as above make be carried on zinc chloride on the silicon-dioxide.Before use, toluene is with 3 dust molecular sieve dryings.Catalyst concn in each reaction sees the following form 13.
(" LRO-90 " is obtained from Lyondell PetrochemicalCompany, and Houston TX), joins in the reaction flask by reinforced dropping funnel with 100g C9 raw material monomer.Just before use, make the C9 raw material monomer carry out drying by activated alumina column (Fischer8-16 order, 0.3g aluminum oxide/ml monomer).Reaction soln is heated to the temperature of reaction shown in the following table 13.By reinforced dropping funnel monomer is added in the reaction flask, it adds speed should be able to keep the desired response temperature under the refrigerative situation outside having.The monomer interpolation time is about 15 minutes.In reaction times of 2 hours altogether under the desired response temperature stirring reaction solution.
After finishing in the reaction times, at room temperature from catalyzer, isolate resin solution by vacuum filtration.With about 100ml toluene drip washing reaction flask and catalyzer filter cake.
Behind the filtering catalyst, sylvic oil is put into a round-bottomed flask, this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of preparation is listed in table 13.
Table 13
Embodiment The catalyzer feeding quantity Temperature of reaction Productive rate Softening temperature (R﹠B) Molecular weight
Mn ?Mw ?Mz ?PD
?59 ?5wt％ 100℃ 41％ 102℃ 530 ?750 ?1440 ?1.4
?60 ?20wt％ 60℃ 38％ 134℃ 790 ?1220 ?4410 ?1.6
?61 ?5wt％ 20℃ 7％ 145℃ 1010 ?1750 ?3950 ?1.8
?62 ?12.5wt％ 100℃ 40％ 107℃ 620 ?810 ?2040 ?1.3
?63 ?12.5wt％ 60℃ 37％ 132℃ 880 ?1210 ?2100 ?1.4
?64 ?20wt％ 100℃ 42％ 105℃ 620 ?810 ?2730 ?1.3
?65 ?12.5wt％ 20℃ 1％ ?- 790 ?2450 ?8260 ?3.1
?66 ?5wt％ 60℃ 18％ 139℃ 910 ?1230 ?2210 ?1.4
?67 ?20wt％ 20℃ 1％ ?- 960 ?2890 ?8040 ?2.8
?68 ?12.5wt％ 60℃ 25％ 122℃ 790 ?1070 ?1950 ?1.4
?69 ?12.5wt％ 60℃ 17％ 123℃ 740 ?960 ?1320 ?1.3
?70 ?5wt％ 136℃ 37％ 88℃ 480 ?600 ?790 ?1.3
?71 ?12.5wt％ 136℃ 41％ 62℃ 390 ?470 ?580 ?1.2
?72 ?20wt％ 120℃ 35％ 80℃ 490 ?580 ?690 ?1.2
Embodiment 73-76
These embodiment illustrate zinc chloride catalyzer and the catalyzer feeding quantity that is carried at various temperatures on the silicon-dioxide, to the influence of the character of prepared C9 resin.Preparation of catalysts
With 20.0g (0.15mol) zinc chloride (98%, Aldrich, Milwaukee, WI) be dissolved in 300ml methyl alcohol (SILVER REAGENT, Aldrich, Milwaukee, WI) in.Adding 80g solid support material in this methanol solution (" EP-12 " silicon-dioxide is obtained from Crosfield Catalysts, Warrington, England).At room temperature stirred slurries 30 minutes.In the vacuum of 2-5mmHg, in rotatory evaporator, remove and desolvate, obtain flowable powder by mild heat.Before use, in drying nitrogen in 2 hours, 100 ℃ of 40 ℃ of calcined catalysts calcining 1 hour, then 150 ℃ of calcinings 2 hours, used calcining all is to carry out in a vacuum.Polyreaction
A 500ml there-necked flask has top agitator, reflux exchanger, gas feed and outlet, thermometer and reinforced dropping funnel.In flask, add 100g toluene (SILVER REAGENT, Aldrich, Milwaukee, WI) and as above make be carried on zinc chloride on the silicon-dioxide.Before use, toluene is with 3 dust molecular sieve dryings.Catalyst concn in each reaction sees the following form 14.
(" LRO-90 " is obtained from Lyondell PetrochemicalCompany, and Houston TX), joins in the reaction flask by reinforced dropping funnel with 100g C9 raw material monomer.Just before use, make the C9 raw material monomer carry out drying by activated alumina column (Fischer8-16 order, 0.3g aluminum oxide/ml monomer).Reaction soln is heated to the temperature of reaction shown in the following table 14.By reinforced dropping funnel monomer is added in the reaction flask, it adds speed should be able to keep the desired response temperature under the refrigerative situation outside having.The monomer interpolation time is about 15 minutes.In reaction times of 2 hours altogether under the desired response temperature stirring reaction solution.
After finishing in the reaction times, at room temperature from catalyzer, isolate resin solution by vacuum filtration.With about 100ml toluene drip washing reaction flask and catalyzer filter cake.
Behind the filtering catalyst, sylvic oil is put into a round-bottomed flask, this flask is equipped with the still head and the thermometer of the band adapter that cooperates inlet tube, and is connected to condenser and receiving bottle.Under nitrogen gas stream, sylvic oil is heated to 235 ℃, feed steam at 235-245 ℃ subsequently, to remove light oil products.Continue to feed steam, the resin of collecting in every 100ml steam condensate is less than 1ml, or up to collecting the 1000ml steam condensate.After cutting off steam, feed nitrogen, so that remove the water in the residual resin at 235 ℃.
The performance of the resin of preparation is listed in table 14.
Table 14
Embodiment The catalyzer feeding quantity Temperature of reaction Productive rate Softening temperature (R﹠B) Molecular weight
??Mn ??Mw ??Mz ????PD
??73 ??10wt％ ??50℃ ??37％ ??134℃ ??830 ??1280 ??2040 ????1.5
??74 ??5wt％ ??50℃ ??21％ ??144℃ ??890 ??1380 ??2260 ????1.6
??75 ??10wt％ ??100℃ ??28％ ??126℃ ??690 ??920 ??1320 ????1.3
??76 ??10wt％ ??50℃ ??35％ ??141℃ ??850 ??1230 ??1890 ????1.5
Although disclose the present invention in conjunction with some embodiment preferred, make its each side more fully be understood and to understand, be not intended to limit the invention in these specific embodiments.On the contrary, its objective is and want in, cover selection scheme, improvement and suitable thing that institute might comprise by the scope of the invention that additional claim limited.

Claims (32)

1, a kind of method for preparing hydrocarbon resin, be included in metal halide solid acid catalyzer on carrier when existing, make and comprise the polymerizable raw material that one of is selected from pure monomer, C5 monomer and the C9 monomer at least and produce hydrocarbon resin, wherein, remove all free associated water basically from described metal halide solid acid catalyzer on carrier.
2, the method for claim 1, wherein be up to about 700 ℃ temperature lower calcination except that anhydrating to be included in from described metal halide solid acid catalyzer on carrier.
3, the method for claim 1, wherein described metal halide on carrier comprises metal halide and carrier, and with described carrier with before metal halide mixes, remove all basically free associated water from carrier.
4, the method for claim 1, wherein described metal halide solid acid catalyzer on carrier comprises the Lewis acid on clay, and described Lewis acid comprises at least a a member that is selected from following group: ZnCl 2, AlCl 3, AlBr 3, BF 3, BCl 3, FeCl 3, SnCl 4, TiCl 4, ZrCl 4, HfCl 4, BiCl 3And lanthanide halides.
5, the method for claim 1, wherein described metal halide solid acid catalyzer on carrier comprises the Lewis acid on silicon-dioxide, and described Lewis acid comprises at least a a member that is selected from following group: ZnCl 2, AlCl 3, BF 3, BCl 3, FeCl 3, SnCl 4, TiCl 4, ZrCl 4, HfCl 4, BiCl 3And lanthanide halides.
6, the method for claim 1, wherein described metal halide solid acid catalyzer on carrier comprises the Lewis acid on silica-alumina, and described Lewis acid comprises at least a a member that is selected from following group: ZnCl 2, AlCl 3, BF 3, BCl 3, FeCl 3, SnCl 4, TiCl 4, ZrCl 4, HfCl 4, BiCl 3And lanthanide halides.
7, the method for claim 1, wherein described metal halide solid acid catalyzer on carrier comprises the Lewis acid on mesoporous silica, and described Lewis acid comprises at least a a member that is selected from following group: ZnCl 2, AlCl 3, BF 3, BCl 3, FeCl 3, SnCl 4, TiCl 4, ZrCl 4, HfCl 4, BiCl 3And lanthanide halides.
8, the method for claim 1, wherein described metal halide solid acid catalyzer on carrier comprises the Lewis acid on mesoporous silica-aluminum oxide, and described Lewis acid comprises at least a a member that is selected from following group: ZnCl 2, AlCl 3, BF 3, BCl 3, FeCl 3, SnCl 4, TiCl 4, ZrCl 4, HfCl 4, BiCl 3And lanthanide halides.
9, the method for claim 1, wherein described metal halide solid acid catalyzer on carrier comprises the Lewis acid on ion exchange resin, and described Lewis acid comprises at least a a member that is selected from following group: ZnCl 2, AlCl 3, BF 3, BCl 3, FeCl 3, SnCl 4, TiCl 4, ZrCl 4, HfCl 4, BiCl 3And lanthanide halides.
10, the method for claim 1, wherein described metal halide solid acid catalyzer on carrier comprises the Lewis acid on zeolite, and described Lewis acid comprises at least a a member that is selected from following group: ZnCl 2, AlCl 3, BF 3, BCl 3, FeCl 3, SnCl 4, TiCl 4, ZrCl 4, HfCl 4, BiCl 3And lanthanide halides, described zeolite comprises at least a a member that is selected from following group: zeolite Y, zeolite beta, MFI, MEL, NaX, NaY, faujusite and mordenite.
11, the method for claim 1, wherein described metal halide solid acid catalyzer on carrier comprises the aluminum halide of polymer graft.
12, the method for claim 1, wherein described raw material comprises pure monomer at least, described pure monomer comprise be selected from vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, 4-vinyl toluene and the Vinyl toluene one of at least.
13, the method for claim 1, wherein, described raw material comprises the C5 monomer at least, described C5 monomer comprises and is selected from iso-butylene, 2-methyl-2-butene, 1-amylene, 2-Methyl-1-pentene, 2-methyl-2-amylene, 2-amylene, cyclopentenes, tetrahydrobenzene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,3-hexadiene, 1, in 4-hexadiene, cyclopentadiene and the Dicyclopentadiene (DCPD) one of at least.
14, the method for claim 1, wherein described raw material comprises the C9 monomer at least, described C9 monomer comprise be selected from vinylbenzene, Vinyl toluene, indenes, Dicyclopentadiene (DCPD) and the alkyl derivative thereof one of at least.
15, the method for claim 1, wherein described raw material contacts in batch reactor with the metal halide solid acid catalyzer on the carrier based on the 0.5 weight %～30 weight % of monomer weight.
16, the method for claim 1, wherein described metal halide solid acid catalyzer on carrier is added in the raw material.
17, the method for claim 1, wherein described raw material is added in the slurries that the metal halide solid acid catalyzer on carrier forms in solvent.
18, the described method of claim 1, wherein, the polymerization under about-50 ℃～150 temperature of reaction of described raw material.
19, the method for claim 1, wherein, described raw material comprises pure monomer at least, and the number-average molecular weight of described hydrocarbon resin (Mn) is about 400～2000, weight-average molecular weight (Mw) is about 500～5000, and Z-average molecular weight (Mz) is about 500～10,000, and the polymolecularity of measuring with Mw/Mn (PD) is for about 1.2～3.5, and wherein Mn, Mw and Mz measure with size exclusion chromatography (SEC).
20, the method for claim 1, wherein, described raw material comprises the C5 monomer at least, and the number-average molecular weight of described hydrocarbon resin (Mn) is about 400～2000, weight-average molecular weight (Mw) is about 500～3500, and Z-average molecular weight (Mz) is about 700～15,000, and the polymolecularity of measuring with Mw/Mn (PD) is for about 1.2～5, and wherein Mn, Mw and Mz measure with size exclusion chromatography (SEC).
21, the method for claim 1, wherein, described raw material comprises the C9 monomer at least, and the number-average molecular weight of described hydrocarbon resin (Mn) is about 400～1200, weight-average molecular weight (Mw) is about 500～2000, Z-average molecular weight (Mz) is about 700～6000, and the polymolecularity of measuring with Mw/Mn (PD) is for about 1.2～3.5, and wherein Mn, Mw and Mz measure with size exclusion chromatography (SEC).
22, a kind of method for preparing hydrocarbon resin is included in zirconium tetrachloride and exists down, makes to comprise the polymerizable raw material that one of is selected from pure monomer, C5 monomer and the C9 monomer at least and produce hydrocarbon resin.
23, method as claimed in claim 22, described raw material comprises pure monomer at least, described pure monomer comprise be selected from vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, 4-vinyl toluene and the Vinyl toluene one of at least.
24, method as claimed in claim 22, wherein, described raw material comprises the C5 monomer at least, described C5 monomer comprises and is selected from iso-butylene, 2-methyl-2-butene, 1-amylene, 2-Methyl-1-pentene, 2-methyl-2-amylene, 2-amylene, cyclopentenes, tetrahydrobenzene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,3-hexadiene, 1, in 4-hexadiene, cyclopentadiene and the Dicyclopentadiene (DCPD) one of at least.
25, method as claimed in claim 22, wherein, described raw material comprises the C9 monomer at least, described C9 monomer comprise be selected from vinylbenzene, Vinyl toluene, indenes, Dicyclopentadiene (DCPD) and the alkyl derivative thereof one of at least.
26, method as claimed in claim 22, wherein, described raw material contacts in batch reactor with the metal halide solid acid catalyzer on the carrier based on the 0.5 weight %～30 weight % of monomer weight.
27, method as claimed in claim 22, wherein, described metal halide solid acid catalyzer on carrier is added in the raw material.
28, method as claimed in claim 22, wherein, described raw material is added in the slurries that the metal halide solid acid catalyzer on carrier forms in solvent.
29, the described method of claim 22, wherein, the polymerization under about-50 ℃～150 ℃ temperature of reaction of described raw material.
30, method as claimed in claim 22, wherein, described raw material comprises pure monomer at least, and the number-average molecular weight of described hydrocarbon resin (Mn) is about 400～2000, weight-average molecular weight (Mw) is about 500～5000, and Z-average molecular weight (Mz) is about 500～10,000, and the polymolecularity of measuring with Mw/Mn (PD) is for about 1.2～3.5, and wherein Mn, Mw and Mz measure with size exclusion chromatography (SEC).
31, method as claimed in claim 22, wherein, described raw material comprises the C5 monomer at least, and the number-average molecular weight of described hydrocarbon resin (Mn) is about 400～2000, weight-average molecular weight (Mw) is about 500～3500, and Z-average molecular weight (Mz) is about 700～15,000, and the polymolecularity of measuring with Mw/Mn (PD) is for about 1.2～5, and wherein Mn, Mw and Mz measure with size exclusion chromatography (SEC).
32, method as claimed in claim 22, wherein, described raw material comprises the C9 monomer at least, and the number-average molecular weight of described hydrocarbon resin (Mn) is about 400～1200, weight-average molecular weight (Mw) is about 500～2000, Z-average molecular weight (Mz) is about 700～6000, and the polymolecularity of measuring with Mw/Mn (PD) is for about 1.2～3.5, and wherein Mn, Mw and Mz measure with size exclusion chromatography (SEC).
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CN106008817A (en) * 2016-06-26 2016-10-12 广西众昌树脂有限公司 Modification method of petroleum resin

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